CN107008223A - Adsorbent of low-load amount high dispersive type benzene refining desulfurization and preparation method thereof - Google Patents
Adsorbent of low-load amount high dispersive type benzene refining desulfurization and preparation method thereof Download PDFInfo
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- CN107008223A CN107008223A CN201710307553.5A CN201710307553A CN107008223A CN 107008223 A CN107008223 A CN 107008223A CN 201710307553 A CN201710307553 A CN 201710307553A CN 107008223 A CN107008223 A CN 107008223A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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- C07C7/00—Purification; Separation; Use of additives
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Abstract
The invention discloses a kind of adsorbent of low-load amount high dispersive type benzene refining desulfurization and preparation method thereof.The adsorbent is mainly made up of activity component metal Ru, aluminum oxide and orthosilicic acid polymer.Metal Ru is mainly dispersed on the outer surface of the polymer-modified alumina support of orthosilicic acid.The prominent features of the adsorbent are the preparation methods for the co-precipitation and dipping for breaching traditional benzene refining desulfuration adsorbent, are firmly assembled in metal Ru on alumina carrier surface by using silicate polymer, make Ru stably high dispersive on adsorbent surface.Compared with prior art, ruthenium base adsorbent Sulfur capacity of the present invention is high, Ru contents are low, stability is high, service life is long, with good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of adsorbent, more particularly to a kind of ruthenium adsorbent of benzene refining desulfurization and preparation method thereof.
Background technology
Benzene is important industrial chemicals, with quite varied industrial use, mainly for the production of dyestuff, medicine, sterilization
Agent, explosive and staple fibre etc..With organic synthesis industrial expansion, the benzaldehyde product of one of chemical industry base stock, its ground are used as
Position is more and more important.One is that demand constantly increases, and two be increasingly harsh to its quality requirement.At present, the master that the industry is present
It is how effectively to remove the organic sulphur components in benzene to want problem.Wherein, absorption desulfurization, which has, invests that small, technique is simple, condition is easy
Control, it is the main method of removing organic sulfur at present both at home and abroad the advantages of desulfurization precision is high.
Chinese invention patent CN 102806062 B, CN 103041766 the A and A of CN 103480325 etc. report in succession
The palladium base adsorbent patent of benzene refining desulfurization.At present, majority uses precious metal palladium in actual industrial, by adding different auxiliary agents,
Either using alkali metal or alkaline-earth metal or rare-earth element modified carrier or using expensive palladium presoma,
So as to improve the desulfurization depth and Sulfur capacity of adsorbent.In view of the economy in commercial Application, the load capacity of Metal Palladium is typically controlled
System determines that it adsorbs Sulfur capacity and can not further improved within 1.0wt%.
Chinese invention patent CN 104941570 A, CN 104307464 A, CN 104841357 A etc. report in succession
The ruthenium base adsorbent patent of benzene refining desulfurization.Compared to Metal Palladium, the market price of metal Ru is about 1/10th of Metal Palladium,
So ruthenium base adsorbent has obvious price advantage relative to palladium base adsorbent.However, being inhaled with ruthenium base made from existing method
Attached dose in use metallic particles tend to coalescence and grow up, so easy in inactivation, large usage quantity, are unfavorable for steady production.
Therefore, the stability of adsorbent how is improved, control Ru particle coalescences are grown up, and reduction metal Ru usage amount is ruthenium base adsorbent face
The key issue faced.
The content of the invention
Key issue to be solved by this invention is in view of the shortcomings of the prior art, providing a kind of high stability, suppressing Ru
Son coalescence is grown up, the adsorbent of high dispersive type benzene refining desulfurization that reduces metal Ru consumption and preparation method thereof.This adsorbent
Be modified by orthosilicic acid, self-assembly method formation high dispersive type ruthenium base adsorbent.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of high dispersive type benzene refining desulfuration adsorbent, it is by active component Ru, structural modification agent orthosilicic acid and aluminum oxide
Carrier is constituted；Si is present in orthosilicic acid, and orthosilicic acid exists in the form of silicate polymer, the network structure of orthosilicic acid polymer
Metal Ru is firmly stable on the surface of alumina support, and metal Ru high dispersives are on adsorbent surface；It is wherein active
Component metals Ru is calculated with the atomicity of its metallic element, and orthosilicic acid is calculated with the atomicity of its Si element, Si and Ru's
Atomicity proportioning is 1~1.5.The load capacity of metal Ru is the 0.32~0.48% of carrying alumina body weight.
A kind of preparation method of low-load amount high dispersive type benzene refining desulfuration adsorbent, it comprises the following steps：
The first step, first imports the 0.05~0.20mol/L configured Ru salting liquids in the reactive tank with stirring,
0.01~0.15mol/L cetyl trimethyl ammonium (CTAB) is added simultaneously, 10~20min is stirred, and then adds reduction
(volume ratio with CTAB is 50~100 to agent n-butanol:1), mixed solution is added in autoclave, in 100~200 DEG C of processing
6~12h, produces metal Ru colloids；
Second step, silester and 0.05~0.3mol/L sodium acetate (or potassium acetate) solution are mixed, then stirred
Under the conditions of mixing, alumina support is added to inside this mixed solution, continues to stir 60~90min at 70 DEG C, by suction filtration, washes
Gained solid is washed in 100 DEG C of dry 6~12h, it is standby；
3rd step, by self-assembly method, is put into autoclave, 0.01~0.04% by sample obtained by the first step, second step
Urea liquid in stir 12h, temperature is 50-90 DEG C, and nitrogen pressure is 0.02~0.4MPa, and mixing speed is 100~200r/
Min, makes the stable high dispersives of metal Ru on alumina carrier surface, then washs gained solid to neutral, vacuum drying,
Produce described ruthenium base adsorbent.
Compared with prior art, the present invention has following advantage：
1. in the present invention, the adsorbent is a shell knot loaded to by the stable metal Ru of orthosilicic acid on aluminum oxide
Structure.The structure can effectively prevent the coalescence of Ru particles from growing up, effectively extension adsorbent service life.
2. metal Ru high dispersives are on alumina carrier surface.Numerous studies have demonstrated that high dispersive type adsorbent agent has
Good absorption property.Benzene refining desulfurization performance is high on adsorbent when the present invention also demonstrate that metal Ru high dispersives.
3. The present invention gives the preparation method of ruthenium base adsorbent, the ruthenium base adsorbent prepared by this method can
In the case of relatively low ruthenium load capacity (0.45%), effective Sulfur capacity reaches 1.31g thiophene/Kg adsorbents.
Brief description of the drawings
Fig. 1 is the process schematic for preparing the stable high dispersive type ruthenium base adsorbent of orthosilicic acid.
Fig. 2 is the TEM figures of the adsorbent prepared by embodiment 1.
Fig. 3 is the TEM figures of the adsorbent prepared by embodiment 2.
Fig. 4 is the TEM figures of the adsorbent prepared by embodiment 3.
Fig. 5 is the TEM figures of the adsorbent prepared by embodiment 4.
Fig. 6 is the TEM figures after the adsorbent use prepared by embodiment 4.
Embodiment
The embodiment and its Figure of description to the present invention elaborate below：
Embodiment 1
The first step, first imports the 0.15mol/L configured ruthenium acetate solution 50mL in the reactive tank with stirring,
0.04mol/L cetyl trimethyl ammonium 15mL is added simultaneously, 15min is stirred, and then adds reducing agent n-butanol
100mL, mixed solution is added in autoclave, is handled 12h at 180 DEG C, is produced metal Ru colloids；
Second step, silester 1.87g and 0.1mol/L sodium acetate solution 285mL is mixed, then in stirring condition
Under, alumina support 200g is added to inside mixed solution, continues to stir 60min at 70 DEG C, suction filtration, washing gained is solid
Body is in 100 DEG C of dry 12h；
3rd step, by self-assembly method, sample obtained by the first step, second step is stirred in 0.01% urea liquid
12h, temperature be 80 DEG C, nitrogen pressure is 0.05MPa, and mixing speed is 100r/min, make metal Ru stably high dispersive in oxygen
Change on alumina supporter surface, gained solid is then washed with distilled water to neutrality, be dried in vacuo, produce described ruthenium base absorption
Agent.
The TEM figures of adsorbent are shown in Fig. 2.Black dot is Ru metallic particles in figure, and is evenly distributed in oxidation aluminium surface.
Embodiment 2
The first step, first imports the 0.15mol/L configured nitric acid ruthenium solution 50mL in the reactive tank with stirring,
0.04mol/L cetyl trimethyl ammonium 15mL is added simultaneously, 15min is stirred, and then adds reducing agent n-butanol
100mL, mixed solution is added in autoclave, is handled 12h at 180 DEG C, is produced metal Ru colloids；
Second step, silester 1.87g and 0.1mol/L sodium acetate solution 285mL is mixed, then in stirring condition
Under, alumina support 200g is added to inside mixed solution, continues to stir 60min at 70 DEG C, suction filtration, washing gained is solid
Body is in 100 DEG C of dry 12h；
3rd step, by self-assembly method, sample obtained by the first step, second step is stirred in 0.01% urea liquid
12h, temperature be 80 DEG C, nitrogen pressure is 0.05MPa, and mixing speed is 100r/min, make metal Ru stably high dispersive in oxygen
Change on alumina supporter surface, gained solid is then washed with distilled water to neutrality, be dried in vacuo, produce described ruthenium base absorption
Agent.
TEM results show, metal Ru high dispersives on the alumina support, see Fig. 3.
Embodiment 3
The first step, first imports the 0.15mol/L configured ruthenium acetate solution 50mL in the reactive tank with stirring,
0.04mol/L cetyl trimethyl ammonium 15mL is added simultaneously, 15min is stirred, and then adds reducing agent n-butanol 75mL,
Mixed solution is added in autoclave, 12h is handled at 180 DEG C, produces metal Ru colloids；
Second step, silester 1.87g and 0.1mol/L sodium acetate solution 285mL is mixed, then in stirring condition
Under, alumina support 200g is added to inside mixed solution, continues to stir 60min at 70 DEG C, suction filtration, washing gained is solid
Body is in 100 DEG C of dry 12h；
3rd step, by self-assembly method, sample obtained by the first step, second step is stirred in 0.01% urea liquid
12h, temperature be 80 DEG C, nitrogen pressure is 0.05MPa, and mixing speed is 100r/min, make metal Ru stably high dispersive in oxygen
Change on alumina supporter surface, gained solid is then washed with distilled water to neutrality, be dried in vacuo, produce described ruthenium base absorption
Agent.
TEM results show, metal Ru high dispersives on the alumina support, see Fig. 4.
Embodiment 4
The first step, first imports the 0.15mol/L configured nitric acid ruthenium solution 60mL in the reactive tank with stirring,
0.04mol/L cetyl trimethyl ammonium 15mL is added simultaneously, 15min is stirred, and then adds reducing agent n-butanol
100mL, mixed solution is added in autoclave, is handled 12h at 180 DEG C, is produced metal Ru colloids；
Second step, silester 1.87g and 0.1mol/L sodium acetate solution 285mL is mixed, then in stirring condition
Under, alumina support 200g is added to inside mixed solution, continues to stir 60min at 70 DEG C, suction filtration, washing gained is solid
Body is in 100 DEG C of dry 12h；
3rd step, by self-assembly method, sample obtained by the first step, second step is stirred in 0.01% urea liquid
12h, temperature be 80 DEG C, nitrogen pressure is 0.05MPa, and mixing speed is 100r/min, make metal Ru stably high dispersive in oxygen
Change on alumina supporter surface, gained solid is then washed with distilled water to neutrality, be dried in vacuo, produce described ruthenium base absorption
Agent.
TEM results show, metal Ru high dispersives on the alumina support, see Fig. 5.Meanwhile, the adsorbent is used for benzin
Desulphurization reaction processed, the adsorbent after use carries out TEM signs, sees Fig. 6.Metal Ru is uniformly dispersed on the alumina support, does not go out
Now significantly build up.
Comparative example 1
External import palladium alumina adsorbant, particle diameter is about 2mm, and precious metal palladium load capacity is 1.0%.
Comparative example 2
Certain domestic company's ruthenium alumina adsorbant, particle diameter is 2mm or so, and noble ruthenium load capacity is 1.0%.
Comparative example 3
The preparation method of the adsorbent, the step of with embodiment 1 and the amount of material that adds keeps constant, its difference exists
In the aluminum oxide in second step is directly used in the synthesis of the 3rd step without processing.
Adsorbent is evaluated using fixed bed reactors, and evaluation method is as follows.
Adsorption reaction is carried out in nitrogen atmosphere, 135~150 DEG C of reaction temperature, 0.8~1.0Mp of pressure, mass space velocity
4h-1.Adsorbent chooses 200g, and Hydrogen activation is first being used using preceding.Raw material is adsorbed from industrial refining benzene addition thiophene, thiophene content
For 1mg/kg, evaluation method is takes above-mentioned industrial refining benzene to flow through adsorbent in the case where specifying reaction condition, then using GB/
T14327-2009 detects the thiophene content after sorbent treatment in benzene.
Evaluation result is as follows：
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, on the premise of design spirit of the present invention is not departed from, technical side of this area ordinary skill technical staff to the present invention
In various modifications and improvement that case is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (3)
1. a kind of high dispersive type benzene refining desulfuration adsorbent, it is characterised in that：It is by active component Ru, structural modification agent orthosilicic acid
With alumina support composition；Si is present in orthosilicic acid, and orthosilicic acid exists in the form of silicate polymer, orthosilicic acid polymer
Network structure stablizes metal Ru on the surface of alumina support securely, and metal Ru high dispersives are on adsorbent surface；
Wherein activity component metal Ru is calculated with the atomicity of its metallic element, and orthosilicic acid is calculated with the atomicity of its Si element,
Si and Ru atomicity proportioning is 1~1.5, and the load capacity of metal Ru is the 0.32~0.48% of carrying alumina body weight.
2. a kind of preparation method of low-load amount high dispersive type benzene refining desulfuration adsorbent, it comprises the following steps：
The first step, first imports the 0.05~0.20mol/L configured Ru salting liquids in the reactive tank with stirring, simultaneously
The cetyl trimethyl ammonium for adding 0.01~0.15mol/L is CTAB, stirs 10~20min, is then adding reducing agent just
(volume ratio with CTAB is 50~100 to butanol:1), mixed solution is added in autoclave, 100~200 DEG C handle 6~
12h, produces metal Ru colloids；
Second step, silester and 0.05~0.3mol/L sodium acetate (or potassium acetate) solution is mixed, then in stirring bar
Under part, alumina support is added to inside this mixed solution, continues to stir 60~90min at 70 DEG C, by suction filtration, washing institute
Solid in 100 DEG C of dry 6~12h, it is standby；
3rd step, by self-assembly method, is put into autoclave, in 0.01~0.04% urine by sample obtained by the first step, second step
12h is stirred in plain solution, temperature is 50-90 DEG C, nitrogen pressure is 0.02~0.4MPa, mixing speed is 100~200r/min,
Make the stable high dispersives of metal Ru on alumina carrier surface, then gained solid is washed to neutral, vacuum drying, produced
Described ruthenium base adsorbent.
3. a kind of preparation method of low-load amount high dispersive type benzene refining desulfuration adsorbent according to claim 1, it is special
Levy and be：Described reducing agent n-butanol and CTAB volume ratio are 50~100:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108514891A (en) * | 2018-05-22 | 2018-09-11 | 上海交通大学 | A kind of preparation method of metal load type multistage pore canal HKUST-1 benzene desulphurization catalysts |
| CN114433003A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN114433004A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Benzene desulfurizer, preparation method and application thereof |
| CN114433005A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Sulfur adsorbent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108514891A (en) * | 2018-05-22 | 2018-09-11 | 上海交通大学 | A kind of preparation method of metal load type multistage pore canal HKUST-1 benzene desulphurization catalysts |
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| CN114433005B (en) * | 2020-10-16 | 2023-08-29 | 中国石油化工股份有限公司 | Sulfur adsorbent, preparation method and application thereof |
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